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61 Fall 2007

Separable Systems

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1

QUANTUM IN
1D Systems
ˆ x ˆ=� d p i dx ⎡ ⎤ = i� ˆ, p ˆ⎦ ⎣x

: SEPARABLE SYSTEMS
� � � ˆ = (x ˆ y ˆ z ˆ+jy ˆ+k z ˆ) = i x ˆ r �� ∂ �� ∂ �� ∂ ˆ= p ˆx p ˆy p ˆz = i p +j +k i ∂x i ∂y i ∂y

3D Systems

(

)

⎡ ˆ, p ˆx ⎤ ⎣x ⎦ = i�

⎡y ˆ, p ˆy⎤ = i� ⎣ ⎦

⎡ ˆz ⎤ ˆ, p ⎣z ⎦ = i�

ˆ 2 −� 2 d 2 ˆ= p T = 2m 2m dx 2 ψ (x)
ˆ = O ˆ ψ ( x ) dx ∫ψ ( x ) O
*

ˆ 2 −� 2 ∂ 2 −� 2 ∂ 2 −� 2 ∂ 2 ˆ= p T = + + 2m 2m ∂x 2 2m ∂y2 2m ∂y 2 ψ ( x, y, z )
ˆ = O ˆ ψ ( x, y, z ) dx dy dz ∫ψ ( x, y, z ) O
*

By fiat, operators corresponding to different axes commute with one another.

ˆ ˆ = yx ˆˆ xy

ˆzy ˆ = yp ˆˆz p

ˆz p ˆx = p ˆx p ˆz p

etc.

Further, operators in one variable have no effect on functions of another: ˆ ( y) = f ( y) x ˆ ˆz f ( x) = f ( x) p ˆz ˆx = p ˆ x f * ( z ) etc. xf p f * (z) p The Time Independent Schrödinger Equation becomes:

⎡ �2 ⎛ ∂ 2 ⎤
∂2 ∂2 ⎞ ˆ ˆ ˆ − + + + V x , y , z ( ) ⎢ ⎥ψ ( x, y , z ) = Eψ ( x, y , z )
⎜ 2 2 2 ⎟ 2 m ∂ x ∂ y ∂ z ⎝ ⎠ ⎣ ⎦ ∇ 2 the Laplacian

⎡ �2 2 ⎤ ˆ, y ˆ, z ˆ ) ⎥ψ ( x, y , z ) = Eψ ( x, y , z ) ⎢ − 2m ∇ + V ( x ⎣ ⎦
�2 2 ˆ ˆ, y ˆ, z ˆ ) Hamiltonian operator in 3D ∇ +V ( x H =− 2m

ˆψ ( x, y , z ) = Eψ ( x, y , z ) H
Separation of variables

3D Schrödinger equation (Time Independent)

z )= ψ x (x )ψ y (y )ψ z (z ) (separation of variables) Where we assume that the 1D functions satisfy the appropriate 1D TISE: ˆ ψ ( x) = E ψ ( x) H x x x x ˆ ψ ( y ) = E ψ ( y ) H y y y y ˆ ψ ( z ) = E ψ ( z ) H z z z z First term: ˆ ψ ( x )ψ ( y )ψ ( z ) = ψ ( y )ψ ( z ) H ˆ ψ ( x ) = ψ ( y )ψ ( z ) E ψ ( x ) H x x y z y z x x y z x x = E xψ x ( x )ψ y ( y )ψ z ( z ) Same for ˆ H y and ˆ H z ⇒ ˆ H = E ψ ψ ˆ ˆ ˆ ⎤ ψ ( x )ψ ( y )ψ ( z )⎤ = ( E + E + E ) ⎡ψ ( x )ψ ( y )ψ ( z )⎤ ⎡H y z x y z ⎣ x y z ⎣ x ⎦ ⎦ ⎣ x + H y + Hz ⎦ ⎡ E = Ex + E y + Ez Thus. y . y. z ) = ⎢ − V x V y V z ( ) ( ) ( ) x y z ⎥ ⎢ 2m ∂y 2 ⎥ ⎢ 2m ∂z 2 ⎥ 2 then ⎣ 2m ∂x ⎦ ⎣ ⎦ ⎣ ⎦ ˆ ˆ ˆ = H + H + H x y z ⇒ Schrödinger’s Eq. y ˆ. the eigenfunctions of the 3D Hamiltonian are just products of the eigenfunctions of the 1D Hamiltonian and the situation is equivalent to doing three separate 1D problems.5. z ) Then try solution of form ψ (x .61 Fall 2007 Separable Systems page 2 IF ˆ. if the Hamiltonian has this special form. ˆ is separable into Conclusion: Wavefunctions multiply and the energies add if H . y. z ˆ ) + Vy ( y ˆ ) + Vz ( z ˆ ) = Vx ( x ˆ) V (x ⎡ �2 ∂ 2 ⎤ ⎡ �2 ∂ 2 ⎤ ⎡ �2 ∂ 2 ⎤ ˆ ˆ ˆ ˆ + + − + + − + H ( x. z ) = Eψ ( x. becomes: ˆ ˆ ˆ ⎤ ⎡H ⎣ x + H y + H z ⎦ψ ( x. y .

ny. ψ n . z )ψ 311 ( x. y. Further. then the two 3D wavefunctions are also orthogonal. for example. z dx dy dz = δ nx . H x y z The 3D product states are naturally normalized if the 1D wavefunctions are normalized: ∫∫∫ψ ( x )ψ ( y )ψ ( z )ψ ( x )ψ ( y )ψ ( z ) dx dy dz = * * * x y z x y z ∫ψ ( x )ψ ( x ) dx ∫ψ ( y )ψ ( y ) dy ∫ψ ( z )ψ ( z ) dz = 1 * * * x x y y z z 1 x 1 x 1 ˆ Notice that for ψ we are free to choose any eigenfunction. while in 1D we usually had one quantum number. z ) dx dy dz ⇒ ∫∫∫ψ 1* ( x )ψ 1* ( y )ψ 1* ( z ) ψ 3 ( x )ψ 1 ( y )ψ 1 ( z ) dx dy dz ⇒ ∫ψ 1* ( x )ψ 3 ( x ) dx ∫ψ 1* ( y )ψ 1 ( y ) dy ∫ψ 1* ( z )ψ 1 ( z ) dz = 0 * x y z x y z x x y y z z 0 x 1 x 1 Because the product states are orthogonal and normalized. y.mz ∫∫∫ ( ) ( ) Example 1:3­D Harmonic Oscillator Let’s consider a particle in 3D subject to a Harmonic potential in x. assume the force constants in each direction are different.nz). ψ ny . y. y.myδ nz .of H y z z Thus. ψ nx . If any one of the three 1D wavefunctions (x. z ψ mxmymz x. in 3D we will have three (nx. we do not have to have all three 1D functions be different. This might be true.y or z) is orthogonal to its counterpart. z ) = ψ x 3 ( x )ψ y1 ( y )ψ z1 ( z ) . y. they’re orthonormal and we summarize this by writing: ψ nxnynz * x. for two product states to be orthogonal. together with any eigenfunction. consider the two wavefunctions ψ 111 ( x.61 Fall 2007 Separable Systems page 3 ˆ =H ˆ +H ˆ +H ˆ . of H x ˆ and any eigenfunction.y and z.5. For example. Multidimensional . of H ˆ . ∫∫∫ψ 111 ( x. y. for a particle trapped inside a protein: the resorting force for moving it in the x direction will be different from y or z because the protein has a different shape along x than y or z (see below right). z ) = ψ x1 ( x )ψ y1 ( y )ψ z1 ( z ) and ψ 311 ( x.mxδ ny . Further.

there are a number of interesting things that can happen that we didn’t see in 1D. z ) = N x H n (α x x ) e 1/2 x y z x − α x x2 2 N y H n y (α y y ) e 1/2 − α y y2 2 − ⎛ αz ⎞ 1/2 N H z e α ( ) z nz z ⎜ ⎟ ⎝π ⎠ 1 4 α z z2 2 1⎞ 1⎞ 1⎞ ⎡⎛ ⎤ ⎡⎛ ⎤ ⎡⎛ ⎤ Enxn y nz = ⎢⎜ n x + ⎟ �ωx ⎥ + ⎢⎜ n y + ⎟ �ω y ⎥ + ⎢⎜ n x + ⎟ �ωz ⎥ 2⎠ 2⎠ 2⎠ ⎣⎝ ⎦ ⎣⎝ ⎦ ⎣⎝ ⎦ ( mk x ) αx = � 12 ωx = kx etc. In either case. m Notice again that for the 3D problem we have 3 quantum numbers. y . because the potential is a sum of an x potential. a y potential and a z potential. For example. the general potential is given by V ( x. and the energy and wavefunction depend on all three simultaneously.5. Based on the discussion above. Degeneracies In 3D. in 3D it is possible for two different . we can immediately write down all the eigenfunctions and eigenvalues: ψ n n n ( x . y to the C­O stretch and z to the H­C­O bend. ky or kz). One example of this is that.61 Fall 2007 Separable Systems page 4 Harmonic potentials are also important for describing the vibrations of polyatomic molecules. in HCO x might correspond to the CH stretch. y . we can easily write the Hamiltonian down as a sum: ˆ =H ˆ +H ˆ +H ˆ H x y z ˆ x2 1 p ˆ ˆ2 + kx x Hx = 2m 2 ˆ y2 1 p ˆ ˆ 2 + ky y Hy = 2m 2 ˆ z2 1 2 ˆ = p ˆ + kz z H z 2m 2 where each 1D Hamiltonian describes a particle subject to a Harmonic potential with the appropriate spring constant (kx. z ) = 1 1 1 k x x 2 + k y y 2 + k z z 2 = V x ( x ) + V y ( y ) + Vz ( z ) 2 2 2 Now.

if our spring constants are all the same: kx = k y = kz ≡ k ⇒ ωx = ω y = ωz ≡ ω 3⎞ ⎛ ⇒ Enxn y nz = �ω ⎜ n x + n y + n z + ⎟ 2⎠ ⎝ 3 The ground state has an energy E000 = 2 �ω . We will typically draw this with a picture like: E E110 E011 E100 E101 … E200 E020 E002 6­fold degenerate E010 E000 E001 3­fold degenerate Non­degenerate Note the wavefunctions are distinct: ψ 100 ( x. nz = 0 . n x = 0. ny = 0. For example. nz = 1 . However. y . y. Suppose we make up a wavefunction that is a sum of two degenerate states. If there are three. z ) ≠ ψ 010 ( x. z ) + b ψ 001 ( x. This never happened for the Particle in a Box or the Harmonic Oscillator. z ) = a ψ 010 ( x. so it is not degenerate. one can show that for bound states in 1D. in 3D we can find degeneracy very easily. z ) ≠ ψ 001 ( x. there are three ways I can get the first excited state energy spring constants to be equal. z ) . they are said to be threefold. one never has degeneracy. There is only one way I can get this energy ( n x = 0. z ) This leads to an interesting effect.61 Fall 2007 Separable Systems page 5 eigenfunctions of the Hamiltonian to have the same energy. y . However.5. ny = 0. n y = 0. every state has its own energy. y. nz = 0 or n x = 0. these two states are called degenerate. So we find that if we choose all the E000 = 3�ω 2 5�ω 2 nondegenerate level 3-fold degenerate level E100 = E010 = E001 = etc. fourfold … degenerate. When this happens. y . nz = 0 ). In fact. ny = 1. y . 5 2 �ω : n x = 1. say ψ ( x. four… states with the same energy.

then the energy levels might look like: E E110 E011 E100 E101 E200 E020 E002 E010 E000 E001 Here. but not quite. ˆψ = H ˆ (a ψ + b ψ ) = a H ˆψ + b H ˆψ H 010 001 010 001 =a 5 �ω 2 ψ 010 + b 5 �ω 2 ω ψ 001 = 5� 2 ( a ψ 010 + b ψ 001 ) ω = 5� 2 ψ This illustrates the important point that any sum of degenerate eigenstates is also an eigenstate of the Hamiltonian with the same eigenvalue. if we choose: kx = k y ≡ k ≠ kz Then the energies become: ⇒ ωx = ω y ≡ ω ≠ ωz 1⎞ ⎛ Enxn y nz = �ω ( n x + n y + 1) + �ωz ⎜ nz + ⎟ 2⎠ ⎝ and we find .e. In this case.5. i. The latter language comes from the pictorial view.61 Fall 2007 Separable Systems page 6 where a and b are constants. Notice that it is possible to break some degeneracies but keep others. because the force constants are slightly different. 010 and 001 states will become non­degenerate. y and z. Setting the spring constants equal amounts to assuming the well is symmetric with respect to x. For example . you can see that the n=1 levels are almost degenerate (they’ve been “split”) and the n=2 levels are almost degenerate. If the symmetry is “broken”. Then it turns out that ψ is also an eigenstate of the Hamiltonian! To see this. k x ≠ k y ≠ k z then the 100. if the spring constants are only slightly different. we will usually say that the degeneracy has been “lifted” or that the degenerate states have been split.

61 Fall 2007 Separable Systems page 7 1 E000 = �ω + �ωz 2 1 E100 = E010 = 2�ω + �ωz 2 3 E001 = �ω + �ωz 2 nondegenerate level 2-fold degenerate level nondegenerate level .5.

..3.. So the solutions to the H x y z 3D equation are products of the 1D solutions ⇒ ψ ( x . y .. y .Vz ( z ) = ∞ Outside the box: − �2 ⎛ ∂ 2 ∂2 ∂2 ⎞ + + ψ ( x.H ˆ are each 1D particle in a box Hamiltonians. y. z ) 2 2 2 ⎟ 2m ⎜ ∂ x ∂ y ∂ z ⎝ ⎠ ψ (x . 2 �2 nx En x = 8m a 2 �2 n y En y = 8m b2 � 2 nz2 En z = 8m c 2 2 nz = 1. y . Where the energy is now a function of all three Quantum numbers: .3. n y = 1.V y ( y ) . z ) = Eψ ( x.. z ) = ψ n ( x )ψ n x y ( y )ψ n ( z ) z where from the 1D problem we have the solutions ⎛n πx⎞ ⎛2⎞ ψ nx ( x ) = ⎜ ⎟ sin ⎜ x ⎟ ⎝a⎠ ⎝ a ⎠ ⎛n πy⎞ ⎛ 2 ⎞2 ψ n y ( y ) = ⎜ ⎟ sin ⎜ y ⎟ ⎝b⎠ ⎝ b ⎠ ⎛2⎞ ⎛n πz⎞ ψ nz ( z ) = ⎜ ⎟ sin ⎜ z ⎟ ⎝c⎠ ⎝ c ⎠ 1 2 1 1 2 n x = 1...3. 2..5. 2.. y . z )= 0 ˆ =H ˆ +H ˆ +H ˆ where We can again apply separation of variables since H x y z ˆ .H ˆ . 2.61 Fall 2007 Separable Systems page 8 Example 2: Particle in 3­D box z c V ( x. z ) = Vx ( x ) + V y ( y ) + Vz ( z ) Vx ( x ) = 0 Vy ( y ) = 0 Vz ( z ) = 0 a x Inside the box: 0≤ x≤a 0≤ y≤b 0≤ z≤c otherwise b y Vx ( x ) .

if a = b = c in our 3­D box: ⇒ En x n y n z = h2 2 n2 + n2 y + nz ) 2 ( x 8ma 3h 2 E111 = 8ma 2 is nondegenerate 1 ⎛ 8 ⎞2 ⎛π x ⎞ ⎛π y ⎞ ⎛π z ⎞ ψ 111 ( x. y . y .61 Fall 2007 Separable Systems page 9 En x n y n z Degeneracies 2 n2 �2 ⎛ nx nz2 ⎞ y = E n x + E n y + E nz = ⎜ 2+ 2+ 2⎟ 8m ⎜ b c ⎟ ⎝a ⎠ Degeneracies occur in a similar fashion for the PiB. z ) = ψ 1 ( x )ψ 1 ( y )ψ 1 ( z ) = ⎜ 3 ⎟ sin ⎜ ⎟ sin ⎜ ⎟ sin ⎜ ⎟ ⎝a ⎠ ⎝ a ⎠ ⎝ a ⎠ ⎝ a ⎠ But… E211 = E121 = E112 h2 = 22 + 12 + 12 ) 2 ( 8ma 3­fold degeneracy Note the wavefunctions are again distinct: ψ 211 (x. e. y . z )≠ ψ 112 (x . z )≠ ψ 121 (x .g. z ) E E222 E221 E211 E212 E121 E111 E122 E112 Non­degenerate Non­degenerate 3­fold degenerate .5. y .

nz = 1.61 Fall 2007 Separable Systems page 10 If the symmetry is “broken”. y . 2..5..3..e.. E112 h2 ⎛ 1 1 4 ⎞ h2 ⎛ 1 4 1⎞ = ⎜ 2 + 2 + 2 ⎟ ≠ E121 = ⎜ 2+ 2+ 2⎟ 8m ⎝ a 8m ⎝ a b c ⎠ b c ⎠ Summary 3­D box ⎛ 8 ⎞2 ⎛ n xπ x ⎞ ⎛ n yπ y ⎞ ⎛ n zπ z ⎞ ψ nx n y nz ( x ..... 2.3. z ) = ⎜ ⎟ sin ⎜ ⎟ sin ⎜ ⎟ ⎟ sin ⎜ ⎝ abc ⎠ ⎝ a ⎠ ⎝ b ⎠ ⎝ c ⎠ En x n y n z 2 n2 h 2 ⎛ nx nz2 ⎞ y = ⎜ 2+ 2+ 2⎟ 8m ⎜ b c ⎟ ⎝a ⎠ 1 n x = 1.. n y = 1. . a≠ b≠c then the degeneracy is lifted. 2.3. i.